Gold-Vanadium Compounds

Why Do We Need to Know This Material The d-block metals are the workhorse elements of the periodic table. Iron and copper helped civilization rise from the Stone Age and are still our most important industrial metals. Other members of the block include the metals of new technologies, such as titanium for the aerospace industry and vanadium for catalysts in the petrochemical industry. The precious metals—silver, platinum, and gold—are prized as much for their appearance, rarity, and durability as for their usefulness. Compounds of d-block metals give color to paint, turn sunlight into electricity, serve as powerful oxidizing agents, and form the basis of some cancer treatments. 

Few gold compounds contain vanadium-carbonyl fragments or dicyclopentadienyl-niobium fragments, respectively, and no additional interactions between discrete heterometalic cores are present in the crystal of any of them. 

Polyhydroxy compounds are oxidized by such metal ions as vanadium(V), chromium(VI), cerium(IV), iridium(IV), and gold(III), among others. These oxidations were found to be catalyzed by acids.171 173 Vanadium(V) and chromium(VI) are closely related in their chemical properties, but the reduction of V(V) is difficult compared with that of Cr(VI) because of its lower redox potential [V(V)-V(IV) = 1.00 V Cr(VI)-Cr(III) = 1.20 V], However, the redox potential increases at lower pH values, facilitating the oxidation of sugars. 

Phillips and Timms [599] described a less general method. They converted germanium and silicon in alloys into hydrides and further into chlorides by contact with gold trichloride. They performed GC on a column packed with 13% of silicone 702 on Celite with the use of a gas-density balance for detection. Juvet and Fischer [600] developed a special reactor coupled directly to the chromatographic column, in which they fluorinated metals in alloys, carbides, oxides, sulphides and salts. In these samples, they determined quantitatively uranium, sulphur, selenium, technetium, tungsten, molybdenum, rhenium, silicon, boron, osmium, vanadium, iridium and platinum as fluorides. They performed the analysis on a PTFE column packed with 15% of Kel-F oil No. 10 on Chromosorb T. Prior to analysis the column was conditioned with fluorine and chlorine trifluoride in order to remove moisture and reactive organic compounds. The thermal conductivity detector was equipped with nickel-coated filaments resistant to corrosion with metal fluorides. Fig. 5.34 illustrates the analysis of tungsten, rhenium and osmium fluorides by this method. 

Anthranilic acid reagent (NH2-C(,H COOH) cerium(IV) oxidizes anthranilic acid to a brown compound. Cerium(III) does not react and must be oxidized first with lead dioxide and concentrated nitric acid to cerium(IV) other oxidizing agents cannot be used, since they react with the anthranilic acid. Iron(III) ions inhibit the test and must be masked by the addition of phosphoric acid. The ions of gold and vanadium, as well as chromate ion, react similarly and therefore interfere. Reducing agents must be absent. 

Other metal complexes of titanium, zirconium, vanadium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver and gold to synthesize a wide variety of interesting new compounds. It utilizes Hoffmann s [51] isolobal relationship between the C=C bond and the metal-carbon triple bond. 

---